JP3006450B2 - Method and apparatus for producing composite material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for producing a composite material in which a sheet-like reinforcing substrate made of a fiber is impregnated with a matrix resin composed of a thermosetting resin, and more particularly to a method and an apparatus for producing a composite material. The present invention relates to a method and an apparatus for producing a fiber-reinforced composite material such as a prepreg by impregnating a sheet-like fiber-reinforced substrate with a thermosetting resin without using a solvent.

[0002]

2. Description of the Related Art As a method for producing a fiber reinforced composite material such as a prepreg, a hot melt method and a solvent method described below have been conventionally known.

[0003] The hot melt method is a two-step process in which a solvent-free resin is used, and the coated paper having good releasability from the resin is once coated and laminated on a sheet-like fiber-reinforced substrate. Is bad, so the cost is high,
Further, the cloth impregnated with the resin was not good when the sheet-like fiber reinforced substrate was heavy.

The solvent method is disclosed in Japanese Patent Application Laid-Open No. 5-320.
As disclosed in Japanese Patent Publication No. 382, for example, in the case of manufacturing a glass cloth epoxy prepreg using a printed board used for an electric insulating material, the viscosity of the resin is reduced by using a solvent, and the resin bath is reduced. Is a method in which a glass cloth is immersed in a glass cloth, the resin is impregnated by capillary action, and then the resin-impregnated glass cloth is dried and semi-cured.

Referring to FIG. 10, a continuous glass cloth 102 is impregnated with a thermosetting resin in a resin tank 103, dried and semi-cured in a drying furnace 105 to form a prepreg 102a, 108
After the crushing, radiant heating is performed by a far-infrared ray furnace 110, and the crushed portion and the crack portion in the vicinity thereof, the whitened portion are smoothed, and immediately thereafter, the cooling roll 109 is used. The prepreg is obtained by smoothing the surface.

However, the above-mentioned solvent method uses a flammable solvent, and thus requires equipment such as a solvent recovery equipment and an explosion-proof equipment. Therefore, the equipment cost is high and a small amount of solvent remains in the prepreg. There were also quality problems due to the occurrence.

[0007]

As a method for producing a fiber-reinforced composite material which solves such a problem, a production method described in Japanese Patent Application Laid-Open No. 5-200748 has been proposed. An apparatus for implementing this manufacturing method is shown in FIG.
As shown in FIGS. 1 and 12, a double belt press 201 is provided, and a feeding unit 202 and an extruder 203 are provided in front of an entrance of the double belt press 201. In the feeding unit 202, a storage roll 204 provided with a glass fiber woven cloth not impregnated with a resin and a storage roll 205 for takeover are located. A winding unit 209 provided with a roll 207 for the prepreg web 206 and a transfer roll 208 is provided behind the duplex belt press 201.

In the above-mentioned apparatus, a glass fiber woven web not impregnated with resin is continuously withdrawn from the storage roll 204 and supplied to the double belt press 201 via the deflecting roller 210. The payout unit 202 is further provided with another storage roll 205, and when the glass fiber woven web of the storage roll 204 ends,
The woven glass fiber web is fed from another storage roll 205. In the extruder 203, the epoxy resin is melted,
The melt passes through the wide slit nozzle of the extruder 203,
It is applied to a woven fiberglass web near the deflection roller 210 as a film.

The layer formed from the woven glass fiber web and the epoxy resin film is then introduced into a double belt press 201 and heated while receiving a surface pressure. At this time, the epoxy resin melt penetrates the glass fiber woven web and further hardens to the B state. At the outlet of the double belt press 201, the prepreg web pre-cured to the B state and impregnated with the epoxy resin is cooled without adhesion from the double belt press 201 and runs out,
It is continuously wound on the roll 207 or 208 of the winding unit 209.

The extruder 203 has, as shown in FIG. 12, an elongated cylinder 218 in which a screw 221 driven by a motor 220 via a reduction transmission 219 is located. I have. The rear part of the screw 221 is a helical recess, which contains the mixture to be melted, consisting of flakes or powder. This mixture is filled in the hopper 222 of the extruder 203. The epoxy resin is further transported by the screw 221,
It is melted during this transport. For this purpose, the cylinder 21
A plurality of heating sleeves 223 are provided so as to surround the heating sleeve 8. As the epoxy resin is conveyed through cylinder 218, the epoxy resin is heated, melted and compressed, so that the epoxy resin forms a homogeneous, viscoelastic melt at the front end of screw 221. The epoxy melt exits through a wide slit nozzle 224 flanged to the front portion of the cylinder 218 as a flat film having a generally square cross section. Then, it is applied to the woven glass fiber web near the deflecting roller 210 as described above, and is introduced into the double belt press 201.

However, in the above-described apparatus, the melt residence time of the epoxy resin in the extruder 203 is long, which may cause a curing trouble in the extruder. The epoxy resin had a high share in the melt state and generated heat due to the share. Further, there is a problem that the film forming property is not good.

Accordingly, it is an object of the present invention to provide a resin having a short melt residence time, eliminating troubles in curing the resin in an extruder, preventing a low shear in a melt state, preventing heat generation due to the shear, and providing a good film-forming property. It is an object of the present invention to provide a method and an apparatus for producing a composite material in which uniform resin impregnation is performed and a composite material having a constant quality can be continuously obtained.

[0013]

The above object is achieved by the method for producing a composite material according to the present invention. In summary, the present invention relates to a method for continuously producing a composite material obtained by coating, impregnating, and smoothing a thermosetting resin on a sheet-like reinforcing substrate made of fibers, wherein (a) substantially removing a solvent. A coating process in which a thermosetting matrix resin that does not contain a molten state is uniformly applied to one surface of a sheet-like reinforcing substrate made of fibers by a die coater, (b) a sheet made of fibers coated with the thermosetting matrix resin Heating the impregnated reinforcing substrate by a non-contact type heating unit, impregnating the matrix resin, and semi-curing the matrix resin; (c) a composite material sheet comprising a semi-cured matrix resin and a sheet-shaped reinforcing substrate composed of fibers Or a step of winding without cutting into a fixed length, and making each step continuous, thereby producing a fiber-reinforced sheet-like composite material.

After the step (a), a step of heating the sheet-like reinforcing substrate made of the matrix resin and the fiber with a non-contact type infrared heater to impregnate the matrix resin into the sheet-like reinforcing substrate made of the fiber. It is preferred to have.

The step of smoothing and homogenizing the matrix resin, in which the sheet-like reinforcing substrate composed of the matrix resin and the fibers is pressed by a plurality of rolls maintaining a constant temperature, comprises at least (a) the coating step and the semi-curing step. It is preferable that the process is provided during the process, or (b) during the semi-curing process, or (c) after the semi-curing process, so that each process is continuous.

While the composition (A) and the composition (B) are introduced into the hopper of the coater from the outlet of the composition in each storage tank, individually or after mixing, the viscosity of each resin is 1000 centipoise. It is preferred to filter at ~ 500,000 centipoise.

According to another aspect of the present invention, there is provided an unwinding unit for a fibrous sheet-like reinforcing base material, an accumulator unit acting upon switching of the fibrous sheet-like reinforcing base material to enable continuous operation, and a thermosetting type. A storage tank for storing the resin-based composition (A) and the curing agent-containing composition (B) in a fluidized state at a constant temperature, an apparatus for measuring each composition from the storage tank, and A mixing unit for preparing a matrix resin by mixing the compositions (A) and (B), a coater unit having a hopper that can be controlled for heating, a sheet-like reinforcing substrate impregnated with the matrix resin, and a half-reduction of the matrix resin. a heating unit of a single or separate cured, pressurizes the matrix resin and the sheet-shaped reinforcing substrate uniformly and smooth, a plurality of roll units which holds the temperature constant, shea Has the preparative composite material wound winding-up unit or a predetermined length of roll-type for the a cutter unit for cutting transversely, continuously producing an apparatus for fiber-reinforced composite material sheet is provided. It is preferable that a filtration unit is provided before the storage tank of the composition (A) and the composition (B), respectively, after the measuring device, or after the mixing unit.

The embodiments of the present invention are as follows.

(1) The sheet-like reinforcing substrate made of fiber is
It is a glass cloth (woven fabric) with a basis weight of 20 g / m ^2.
１０００1000 g / m ² .

(2) The matrix resin comprises a bisphenol-type epoxy resin containing bromine, a curing agent and a curing accelerator.

(3) The viscosity of the matrix resin substantially containing no solvent at the time of coating is from 1000 centipoise to 5000 centipoise.
00 centipoise.

(4) The composition (A) and the composition (B)
In each storage tank, or during the introduction from each storage tank to the hopper of the coater, the viscosity of each resin is defoamed at 1,000 to 500,000 centipoise.

(5) The composition (A) and the composition (B)
While the resin is being introduced into the hopper of the coater from the outlet of the resin in each storage tank, the resin is filtered individually or after mixing with a viscosity of 500000 to 1000 centipoise.

(6) When the composition (A) and the composition (B) are mixed in a mixer and coated by a coater, the average residence time of the resin from the inlet of the mixer to the outlet of the coater is less than 20 minutes. It is.

(7) As a coater unit, a gear pump for measuring resin is provided in the coater, and a gear pump-in-die type coater in which the ratio of the resin streamline of the gear pump to the resin streamline of the coating section is less than 3 is provided. It is.

(8) The non-contact type heater in the impregnation step is an infrared heater having a wavelength of about 1 μm to 10 μm, or a floating type heating unit for injecting a heating fluid from above and below the base material from a plurality of nozzles. It is.

(9) The non-contact type heating unit in the semi-curing step is a floating type in which a heating fluid is jetted from above and below the base material from a plurality of nozzles.

(10) The heating fluid is air or nitrogen.

(11) In the heating unit of the floating type, the impregnation step is performed in the first half and the semi-curing step is performed in the second half.

(12) In the impregnation step using a non-contact type heating unit, heating is performed at an ambient temperature of 120 to 300 ° C. for a processing time of 3 to 120 seconds.

(13) In the semi-curing step using a non-contact type heating unit, heating is performed at an ambient temperature of 120 to 200 ° C. and a processing time of 20 to 300 seconds.

[0032]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A method and an apparatus for producing a composite material according to the present invention will be described below in more detail with reference to the drawings.

First, referring to FIG. 1, a description will be given of a composite material manufacturing apparatus for implementing the method of manufacturing a composite material according to the present invention. In the following description, it is assumed that an epoxy resin is used as a matrix resin for a glass cloth base material and impregnated to continuously produce a prepreg.

FIG. 1 schematically shows an apparatus for producing a prepreg. This apparatus is provided with an unwinding device 1 for unwinding the glass cloth substrate A at the left end in the figure, and a winding device 12 for winding the prepreg B at the right end. The unwinding device 1 includes a roller 1 'and a takeover roller 1 ", and the winding device 12 similarly includes a roller 12' and a roller 12". Roller 1 'and takeover roller 1 "adjacent to the unwinding device 1 to enable continuous operation
An accumulator 2 acting when switching between the two is provided, and a hard chrome-plated backup roller 8 is arranged next to the accumulator 2.

On the other hand, the present apparatus comprises an epoxy resin, a curing agent,
A matrix resin supply device R for melting, mixing and measuring the resin composition containing a curing accelerator and the like is provided. The matrix resin supply device R is connected to a gear pump-in-die type coater 7 via a hopper 6. ing. Further, a backup roller 8 is provided so as to face and close to the lip portion of the coater 7.

In the backup roller 8, an epoxy resin containing a curing agent, that is, a matrix resin is applied to one surface of the glass cloth base material A supplied from the accumulator 2 by the coater 7 with a uniform thickness.

The backup roller 8 is made of polytetrafluoroethylene (PTFE) or a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (P) in order to improve the releasability with the resin on the surface of the metal roller.
FA), a fluororesin typified by hexafluoropropylene-tetrafluoroethylene copolymer (FEP), a silicone rubber, or the like, but is not limited thereto. The back-up roller 8 is preferably of a jacket type, in which a predetermined liquid medium is circulated in the jacket so that the temperature can be controlled to a constant value, but the invention is not limited to these.

An infrared heater 9 is provided adjacent to the backup roller 8 for impregnating the matrix cloth A with the matrix resin. The infrared heater 9 is a non-contact type heater in which heaters are provided at an upper portion and a lower portion, and a material to be heated passes through an intermediate portion. The infrared heater 9 preferably has a wavelength of about 1 μm to 10 μm.

Further, next to the infrared heater 9, compaction rollers 15, 15 'whose temperature is kept constant.
Is provided, and the glass cloth substrate impregnated with the matrix resin is pressed by the infrared heater 9 to be uniform and smooth.

It is necessary to suppress the adhesion of the resin to the rollers 15, 15 '. In order to reduce the adhesiveness between the rollers 15, 15' and the resin, the rollers 15, 15 'are coated with Teflon or covered with silicone rubber. Special processing by such as is given.

Next, a floating dryer 10 for semi-curing the matrix resin impregnated in the glass cloth substrate A is provided.

The floating dryer 10 is of a non-contact type, and as shown in FIG.
0a, a heating fluid is injected from above and below the substrate A,
Is heated in a state where is floated. Air or nitrogen is preferred as the heating fluid.

Next to the floating roller 10, a cutter device (not shown) for cutting the composite sheet B to a predetermined length is provided.

The coater 7 of the gear pump-in-die type employed in the present apparatus, as shown in FIG. 9, the ratio of the resin flow line L ₂ of the resin flow line L ₁ and the coater lip of the gear pump 0.9 <is set to L ₂ / L ₁ <3.

As a result, the flow of the resin in the width direction inside the die is eliminated, and the discharge at the lip is made uniform. Since the gear pump is arranged very close to the lip portion, the internal pressure of the resin rises quickly and has a quick rise of coating. Substrate loss required for startup is approximately 1/3 to 1/5 as compared with a conventional die coater. In addition, the coating material before the pump cannot be discharged, resulting in all losses, but the loss of the coating material is small. Furthermore, since it has an integrated structure, it has many advantages such as easy uniform heating with a heat medium or the like.

Next, a method of manufacturing a prepreg using the prepreg manufacturing apparatus configured as described above will be described.

First, a matrix resin obtained by melting, mixing, and measuring a resin composition containing an epoxy resin, a curing agent, a curing accelerator, and the like from a matrix resin supply device R is supplied via a hopper 6 to a gear pump-in-die type coater. 7 is supplied.

On the other hand, the glass cloth substrate A wound around the unwinding device 1 is supplied to the backup roller 8 via the accumulator 2, and the matrix resin discharged from the coater 7 is used for the glass cloth substrate A. It is applied uniformly on one side.

The glass cloth substrate used was 20 g /
A basis weight of m ^{2 to} 1000 g / m ² can be applied.

After mixing the main resin of the epoxy resin and the resin containing the curing agent and the curing accelerator, the residence time until the mixture is discharged from the lip portion of the coater 7 is 2 hours.
Preferably, it is less than 0 minutes. This is because if the time exceeds 20 minutes, the curing reaction partially proceeds, making it difficult to make the quality uniform and stable production, and more preferably less than 15 minutes.

The viscosity of the resin at the time of the above coating is 1
000 centipoise (hereinafter abbreviated as cP) to 500,000
It is preferably cP. If the pressure is less than 1000 cP, the metering stability of the resin by the gear pump will be poor, and the viscosity will be too low to impregnate the sheet-like reinforcing substrate made of fiber too much and penetrate to the back surface, and the resin will adhere to the backup roll. This is because stable running becomes difficult. On the other hand, if it exceeds 500,000 cP, the spreadability of the resin deteriorates, and it becomes difficult to apply a uniform coating to the sheet-like reinforcing material made of fibers.

Next, while the glass cloth substrate A coated with the matrix resin passes through the inside of the infrared heater 9, the matrix resin is impregnated into the glass cloth substrate A, and is further applied by the compaction rollers 15, 15 '. Pressed, uniform and smooth. In this case, since the heat history to the resin is small and the curing reaction does not proceed, the pressure can be smoothed under a low pressure, so that the bending of the glass cloth can be suppressed.

Next, the matrix resin is semi-cured while passing through the floating dryer 10.

The ambient temperature of the floating dryer 10 is 120 ° C. to 200 ° C., and the processing time is 20 seconds to 300 seconds.

Next, the composite material sheet B obtained through the floating dryer 10 is cut into a predetermined size by a sheet cutting device (not shown).

In addition to cutting the composite material sheet B as described above, the composite material sheet B can be wound into a roll.

Note that, instead of the matrix resin supply device R, a configuration as shown in FIG. 2 may be used. That is, a main storage tank 3 for storing a main agent of an epoxy resin and a sub-storage tank 3 'for storing a resin containing a curing agent and a curing accelerator are provided, and the main agent and the curing agent are measured in the respective tanks 3 and 3'. The measuring pumps 4 and 4 'for the measurement are connected. Further, a static mixer 5 having a 12 to 24 stage static mixer for uniformly mixing the composition containing the epoxy resin base material and the curing agent and obtaining a desired matrix resin is connected to the metering pumps 4 and 4 ". In this configuration, a gear pump-in-die type coater 7 is connected to the mixer 5 via a hopper 6. The other configuration is the same as the configuration of the apparatus shown in FIG.

In such a configuration, the main storage tank 3 contains the main agent of the epoxy resin and the sub-storage tank 3 ′ stores the resin containing the curing agent and the curing accelerator in a fluidized state. 'Respectively connected to the metering pumps 4,
After weighing a predetermined amount by 4 ', the mixture is uniformly mixed by a static mixer 5 to obtain a matrix resin. The matrix resin is further supplied to a gear pump-in-die type coater 7 via a hopper 6.

The die coater used in the present invention is preferably a die coater capable of controlling the resin to be discharged from the lip portion in a uniform distribution state. In addition to the gear pump-in-die type die coater described above, ,
An ultra coat die type die coater may be used.

In this ultra coat die type coater, the lip surface of the die lip and the material to be coated (glass cloth substrate) are extremely close to each other but not in contact with each other. (Resin) is interposed and flows. The matrix resin discharged from the lip slot flows out between the lip surface and the glass cloth substrate. At this time, since the glass cloth substrate always moves in a certain direction at a constant speed, the matrix resin actually passes between the lip surface and the glass cloth substrate. In other words, when the matrix resin passes through the gap between the lip surface and the glass cloth base material at a certain flow rate, a large shear stress is applied, causing a sudden change in viscosity and giving a certain film forming force, and the glass cloth It is smoothly applied on the substrate. At this time, the flow rate of the matrix resin is determined by the pumping amount and the speed of the glass cloth substrate.

The roll unit such as a compaction roller may be placed before or after the semi-curing step, or at any point between the divided semi-curing steps. Also, they may be arranged at a plurality of locations at the same time.

Further, as a non-contact heating unit which can be used in the step of impregnating the matrix resin into the sheet-like reinforcing base material, a hot air circulation heater or the like can be used in addition to the infrared heater.

As the matrix resin, a thermosetting resin such as an unsaturated polyester resin, a polyurethane resin, and a vinyl ester resin can be used in addition to the epoxy resin.

Examples of the sheet-like reinforcing material include cloth of glass fiber, organic fiber such as aromatic polyamide fiber and aromatic polyester fiber, cloth of glass fiber and carbon fiber, and one-way arrangement fiber sheet, and random arrangement. Non-woven sheets can also be used.

Example 1 Next, Example 1 of a manufacturing method using an apparatus configured as shown in FIG. 2 will be described in detail.

A glass cloth substrate having a thickness of 180 μm and a basis weight of 205 g / m ² (WE-18K-B manufactured by Nitto Boseki Co., Ltd.)
Y-58) was supplied from the unwinding device 1 via the accumulator 2 to the backup roller 8 for coating with a coater.

On the other hand, a composition A mainly composed of a bisphenol epoxy resin containing bromine, which is maintained in a liquid state at 60 ° C. in a main storage tank 3, is measured by a measuring pump 4, and maintained at 60 ° C. in a sub storage tank 3 ′. Curing agent dicyandiamide (D
A matrix obtained by mixing the epoxy resin composition containing ICY) and the epoxy resin composition B containing a curing accelerator, which is measured by a measuring pump 4 ', with a mixer 5 at a residence time of 1 minute in the mixer. The resin was adjusted and supplied to a hopper 6 kept at 60 ° C.

The resin supplied to the hopper 6 is measured by a gear pump-in-die coater (L ₂ / L ₁ = 1.1) 7 and the resin amount is 145 g at a lip portion of the coater on the glass cloth substrate at a resin viscosity of 10,000 cP. / M ² was applied to a uniform thickness and sent out to the infrared heater 9 by the backup roller 8. At this time, the residence time of the resin from the inlet of the mixer to the outlet of the coater was 10 minutes.

Next, in the infrared heater 9, the ambient temperature at the center of the infrared heater 9 was controlled to 150 ± 3 ° C.
For 5 seconds to impregnate the resin coated on the upper surface of the glass cloth substrate A from the inside of the glass cloth to the lower surface.

Then, a pressure of 5 kg / kg is applied by the compaction rollers 15 and 15 ′ whose surface temperature is controlled to 50 ± 3 ° C.
Pressurization was performed at a pressure of cm ² , and homogenization was performed by applying a mechanical pressure.

Further, as shown in FIG. 8, a plurality of nozzles 10a for injecting a heated gas up and down are provided, and a floating dryer 1 in which the ambient temperature is controlled to 160 ± 1 ° C.
0, the resin was run for 60 seconds to perform a semi-curing step.

As a result, a fiber reinforced sheet-like composite material in which a thermosetting resin was impregnated into a glass cloth base material, a so-called prepreg, was wound by the winding device 12.

In this apparatus, the epoxy resin base material and the composition containing the curing agent are separately measured and supplied, and quickly mixed by the static mixer, so that the residence time of the melt is shortened and the curing trouble in the coater is reduced. Can be prevented.

Further, since the extruder is a gear pump-in-die type coater which does not have the conventional elongated cylinder and screw, the extruder has a low share in a melt state, and does not generate heat due to the share. Good film properties.

The obtained sheet-like composite material had good uniformity of thickness and good impregnation of the resin into the glass cloth base material. When the surface was observed with a magnifying glass of 30 times, no void was observed. Was. The curing reaction rate indicating the degree of semi-curing was 48%, and the tackiness was good.

Comparative Examples 1, 2, and 3 Next, as a comparative example with the above-mentioned Example 1, a coating method using a gear pump-in-die type coater was used instead of the coating method shown in FIG.
A case where a coating method using a top feed reverse roll coater as shown in FIG. 3 is employed will be described.

In the case of this comparative example, three rolls (melting / measuring roll 8a, coater roll 8) having an effective length of 550 mm
b. A composition using a top-feed reverse roll coater composed of a backup roll 8) and containing the same epoxy resin base such as the same brominated epoxy resin used in Example 1 and a curing agent composed of dicyandiamide and an imidazole compound. By changing the melting temperature, the melt viscosity was changed to 8000 cP, 20,000 cP, and 50,000 cP, and the same kind of thickness as that used in Example 1 was used.
A glass cloth substrate having a basis weight of 205 g / m ² (WE-18K-BY-58 manufactured by Nitto Boseki Co., Ltd.) was supplied to the roll coater from the unwinder, and coated with a resin at a coating width of 500 mm and a running speed of 10 m / min. A work amount of 145 g / m ^{2 was} applied and wound.

The results shown in Table 1 below were obtained as to the coating state, the loss of the resin on the back surface of the glass cloth, the adhesion to the backup roll, and the running windability. Stable coating was difficult under any of the conditions.

[0079]

[Table 1]

Examples 2 to 10; Comparative Examples 4 to 7 The same method as in Example 1 was applied to the apparatus shown in FIGS. 2 and 3, and only the type, temperature, and processing time of the heater for performing the impregnation step were changed. Manufactured a prepreg under exactly the same conditions as in Example 1. The apparatus shown in FIG. 3 employs a floating dryer 9 'instead of the infrared heater 9 shown in FIG. As a result, the results shown in Table 2 were obtained.

[0081]

[Table 2]

Examples 11 to 14; Comparative Examples 8 and 9 In Example 14, the same conditions as in Example 1 were used except that the atmosphere temperature and the treatment time during semi-curing were changed. Manufactured. A prepreg was manufactured by changing the atmosphere temperature and the traveling speed by changing the hot air temperature to change the heat treatment time by using a device having 20 floating nozzles shown in FIG. Thereby, the results shown in Table 3 below were obtained.

[0083]

[Table 3]

Example 15 The apparatus of Example 15 has the same structure as that of Example 1, but as shown in FIG. 4, the compaction roller 15 next to the infrared heater 9 for performing the impregnation step.
15 'is omitted, and compaction rollers 11, 11' are arranged next to the floating roller 10 in the first embodiment.

With such a configuration, the glass cloth base material in which the matrix resin has been semi-cured while passing through the inside of the floating dryer 10 is applied to the compaction roller 1.
The fiber is pressurized by 1, 11 ′, and is uniformly and smoothed to obtain a fiber-reinforced sheet-like composite material, so-called prepreg.

Embodiment 16 The apparatus of Embodiment 16 has a configuration substantially similar to that of Embodiment 15, but as shown in FIG. 5, a floating dryer for performing a semi-curing step is divided into front and rear portions 10a and 10b. And the compaction rollers 16, 16 '
It is characterized by having attached.

With this configuration, the sheet-like reinforcing base made of resin-coated fiber is heated by the infrared heater 9 to impregnate the base with the resin, and then semi-cured by the front floating roller 10a. Is pressed and uniformized and smoothed by a plurality of rollers 16 and 16 ′, and semi-cured again by the floating roller 10 b.

In the case of this embodiment, there is an effect that the pressure applied by the compaction roller is maintained at an appropriate level, and the adhesion of the resin to the compaction roller is suppressed.

Example 17 The apparatus of Example 17 is an apparatus having a configuration substantially similar to that of Example 1, but as shown in FIG.
And a hopper 6 connected to a gear pump-in-die type coater 7.

In the filtration unit 14, the mixer 5
The bubbles generated in the above are removed, that is, defoaming is performed to prevent generation of voids in the resin, and at the same time, filtration is performed to remove impurities. Thereby, the quality of the prepreg to be manufactured can be improved.

The viscosity of the resin passing through the filtration unit 14 is preferably from 1,000 cP to 500,000 cP. This is because it is necessary to increase the melting temperature in order to make the viscosity of the resin 1000 cP or less, and if the melting temperature is too high, curing starts during the melt retention, making uniform quality and stable production difficult. That's why. Also, 50,000
If it exceeds 0 cP, the pressure loss during resin transfer, defoaming and filtration becomes too large, and smooth transfer, efficient defoaming and filtration cannot be performed.

The filtering unit may be arranged so as to perform filtration before filling the main storage tank 3 and the sub-storage tank 3 ′ with resin.

Example 18 The device of Example 18 is a device having substantially the same configuration as that of Example 15, but as shown in FIG. 7, the infrared heater 9 in Example 1 was omitted, and the floating dryer 10 was used. However, the impregnation step and the semi-curing step are also performed. In this case, the impregnation step is performed in the first half of the floating dryer 10 and the semi-curing step is performed in the second half.

A relatively low-weight glass cloth (about 20 to 2)
00g / m ² ) lower resin viscosity of 1,000 to 10,000
In the case of coating with cP, even if the infrared heater 9 is omitted, the impregnation of the resin proceeds, and the impregnating property is good because the heating effect near the entrance of the floating dryer 10 is taken into consideration.

Example 19 In Example 19, the same glass cloth base material, resin composition and equipment as in Example 1 were used, and the resin streamline L ₁ of the gear pump of the gear pump-in-die type coater was used.
And it was verified for the presence of abnormal retention of the resin in the coater ratio of the resin flow line L ₂ of the coater lip and various modifications.

[0096] The presence or absence of abnormal residence of the resin in the coater was determined by using a resin composition obtained by uniformly mixing a 0.1% by weight of a blue dye with the resin composition, and then using a non-colored resin composition. After discharging the resin volume of three times as much as the residence volume of the resin in the coater lip from the output of the gear pump, the coater was opened and the color distribution was visually judged. The results were as follows.

[0097]

[Table 4]

As is apparent from Table 4, the ratio L ₂ / L ₁ of the resin streamline L ₁ of the gear pump of the coater to the resin streamline L ₂ of the coater lip portion is most preferably 1.1. Understand.

[0099]

As is clear from the above description, according to the method for producing a composite material according to the present invention, the residence time of the melt is short, the trouble of curing the resin in the extruder is eliminated, and the share of the melt state is low. This prevents heat generation due to heat generation, and further improves the film-forming properties, enables uniform resin impregnation, and continuously obtains a composite material having a constant quality.

The same effect can be obtained by the apparatus for manufacturing a composite material according to the present invention.

[Brief description of the drawings]

FIG. 1 is a configuration diagram showing a manufacturing apparatus for performing a method for manufacturing a composite material according to the present invention.

FIG. 2 is a configuration diagram showing a manufacturing apparatus for performing a method for manufacturing a composite material according to the present invention, to which the methods of Examples 1 to 6 and Comparative Examples 4 and 5 are applied.

FIG. 3 is a configuration diagram illustrating a manufacturing apparatus to which the methods of Examples 7 to 10 and Comparative Examples 6 and 7 are applied.

FIG. 4 is a configuration diagram illustrating a fifteenth embodiment of a manufacturing apparatus.

FIG. 5 is a configuration diagram illustrating a sixteenth embodiment of a manufacturing apparatus.

FIG. 6 is a configuration diagram illustrating a seventeenth embodiment of a manufacturing apparatus.

FIG. 7 is a configuration diagram showing an eighteenth embodiment of the manufacturing apparatus.

FIG. 8 is a schematic sectional view showing a nozzle of a floating heater applied to the manufacturing apparatus of the embodiment.

9 is an explanatory diagram showing a ratio of a resin streamline of a gear pump of the coater in FIG. 1 to a resin streamline of a coating section.

FIG. 10 is a schematic configuration diagram showing a first example of a conventional manufacturing apparatus.

FIG. 11 is a perspective view showing a second example of a conventional manufacturing apparatus.

FIG. 12 is a sectional view of a main part of the manufacturing apparatus of FIG. 10;

FIG. 13 is a main part configuration diagram of a top feed reverse roll coater used in Comparative Examples 1, 2, and 3.

[Explanation of symbols]

1 Unwinding unit 2 Accumulator unit 3 Main storage tank 3 'Secondary storage tank 4 Measuring pump (Measuring device) 4' Measuring pump (Measuring device) 5 Mixer (Mixing unit) 6 Hopper 7 Gear pump-in-die type coater (Coater unit) Reference Signs List 8 backup roller 9 infrared unit (impregnation unit) 10 floating dryer (heating unit) 11 compaction roller (roll unit) 12 winding unit 14 filtration unit

Continued on the front page (72) Inventor Takayuki Fukuda 1-3-1 Nishitsurugaoka, Oimachi, Iruma-gun, Saitama Prefecture (72) Inventor Hiroshi Toshima 1-3-1 Nishitsurugaoka, Oimachi, Iruma-gun, Saitama (56) References JP-A-6-190930 (JP, A) JP-A-4-187430 (JP, A) JP-A-6-143447 (JP, A) JP-A-4-84556 (JP, U) (58) Field surveyed (Int. Cl. ⁷ , DB name) B29C 70/00-70/88

Claims (7)

(57) [Claims] 1. A method for continuously producing a composite material obtained by coating, impregnating, and smoothing a thermosetting resin on a sheet-like reinforcing substrate made of fibers, wherein (a) heat-free material containing substantially no solvent. A coating step of uniformly coating the curable matrix resin on one side of a sheet-like reinforcing substrate made of fibers by a die coater in a molten state; (b) a sheet-like reinforcing base made of fibers coated with a thermosetting matrix resin Heating the material with a non-contact type heating unit, impregnating the material, and semi-curing the matrix resin , and (c) fixing a composite material sheet of the semi-cured matrix resin and a sheet-like reinforcing base material composed of fibers to a certain degree. A method for producing a fiber-reinforced sheet-like composite material, comprising a step of cutting to a length or winding without cutting, and making each step continuous. 2. After the step (a), the sheet-shaped reinforcing substrate made of a matrix resin and a fiber is heated by a non-contact type infrared heater to impregnate the matrix resin into the sheet-shaped reinforcing substrate made of a fiber. The method according to claim 1, further comprising a step. 3. The step of smoothing and uniformizing a matrix resin in which a sheet-like reinforcing substrate made of a matrix resin and fibers is pressed by a plurality of rolls maintaining a constant temperature, comprises at least (a) the coating step and The method according to claim 1, wherein each step is provided during the semi-curing step, or (b) during the semi-curing step, or (c) after the semi-curing step, and the respective steps are made continuous. Production method. 4. As the thermosetting resin, an epoxy resin composition (A) mainly composed of one or two or more kinds of components, and an epoxy composition (B) containing at least a curing agent are used. 2. The method according to claim 1, wherein the matrix resin is maintained in a fluidized state, weighed, uniformly mixed to form a matrix resin, and the matrix resin is supplied to a coater.
Manufacturing method. 5. The composition (A) and the composition (B) are introduced into the hopper of the coater from the outlet of the composition in each storage tank individually or after mixing. 5. The method according to claim 4, wherein the filtration is performed at 1,000 to 500,000 centipoise. 6. An apparatus for carrying out the method according to claim 1, comprising: an unwinding unit for the fibrous sheet-like reinforcing base material; and an accumulator unit acting when the fibrous sheet-like reinforcing base material is switched to enable continuous operation. A storage tank for storing the composition (A) containing a thermosetting resin as a main component and a composition (B) containing a curing agent in a fluidized state at a constant temperature, and an apparatus for measuring each composition from the storage tank A mixing unit for preparing a matrix resin by mixing the weighed compositions (A) and (B), a coater unit having a hopper that can be heated and controlled, and impregnating the matrix resin into a sheet-like reinforcing substrate;
And a single or separate heating unit for semi-curing the matrix resin, and a plurality of roll units for maintaining uniform temperature by pressing the matrix resin and the sheet-shaped reinforcing base material uniformly and smoothly. An apparatus for continuously producing a fiber-reinforced sheet-like composite material, comprising: a roll-type winding unit for winding the sheet-like composite material; 7. A filter unit is provided before the storage tanks of the composition (A) and the composition (B), respectively, after the measuring device, or after the mixing unit.
Equipment.